Nonchromophoric Organic Matter Suppresses Polycyclic Aromatic

Feb 16, 2014 - Our results support previous reports that bulk ice and ice surfaces present distinct reaction environments, and show for the first time...
0 downloads 0 Views 408KB Size
Download PDF
Article pubs.acs.org/JPCA

Nonchromophoric Organic Matter Suppresses Polycyclic Aromatic Hydrocarbon Photolysis in Ice and at Ice Surfaces Philip P. A. Malley and Tara F. Kahan* Department of Chemistry, Syracuse University, 1-014 Center for Science and Technology, Syracuse University, Syracuse, New York 13244, United States ABSTRACT: We have investigated the effects of organic matter (OM) that does not absorb sunlight (“nonchromophoric”) on the reactive environment presented by bulk ice and ice surfaces. Fluorescence spectroscopy showed that the presence of as little as 2.5 × 10−4 M octanol or decanol reduces the extent to which naphthalene self-associates at ice surfaces, which indicates that naphthalene partitions between ice and organic phases present there. We also measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene, pyrene, and phenanthrene in bulk ice and at ice surfaces containing 2.5 × 10−5 M to 7.5 × 10−3 M OM. In bulk ice, even the lowest concentrations of OM reduced photolysis kinetics to below our detection limits. Organic matter also reduced measured photolysis kinetics of PAHs at ice surfaces, but generally to a lesser extent than in bulk ice. Our results support previous reports that bulk ice and ice surfaces present distinct reaction environments, and show for the first time that OM can affect PAH photolysis kinetics by altering the physical environment within bulk ice and at ice surfaces.

■

rates.13,17−19 In bulk ice, solutes that photolyze to form hydroxyl radicals increased measured PAH reaction rates,12,16,20 but no enhancement was observed at ice surfaces.12,17 Sodium chloride and sodium bromide have been shown to decrease photolysis rates of the aromatic compound harmine at ice surfaces due to the formation of a liquid brine at the ice surface; at high salt concentrations, harmine photolysis kinetics were the same as those measured in liquid water.19 These studies show that solutes can greatly alter the reaction environment in ice and at ice surfaces. Organic species are often associated with natural waters and with snow and ice in the atmosphere (e.g., refs 5, 21). Immiscible organic species form coatings at water surfaces that can significantly affect reaction kinetics there. The mass transfer of gas-phase species to water can be enhanced or suppressed by organic films, as can heterogeneous reactions such as hydrolysis and ozonation (e.g., refs 22−26). Chromophoric dissolved organic matter (cDOM) absorbs solar radiation, and so can affect photochemistry in aqueous solution by filtering sunlight, by acting as a photosensitizer, or by producing reactive species such as hydroxyl radicals (e.g., ref 27). Organic matter that does not absorb sunlight (nonchromophoric OM) may also affect photochemistry: We have recently shown that PAH photolysis in aqueous solution is suppressed by miscible organic species such as methanol.28 Immiscible OM may also affect photochemistry by forming microenvironments in natural waters to which hydrophobic pollutants can partition; the fate of

INTRODUCTION A wide range of atmospherically important reactions occur in snow and ice at Earth’s surface (e.g., refs 1−6). Reactions in ice occur primarily in two compartments: veins and pockets within the ice bulk, which contain liquid water,7 and at the ice surface, which has physicochemical properties that are distinct from both bulk ice and liquid water (e.g., refs 7−11). Some reactions have been shown to proceed at different rates in these two regions.12,13 Reaction kinetics in ice have been measured primarily in samples prepared from deionized water. This minimizes experimental artifacts and simplifies the reaction system, but may not accurately represent the reaction environment that ice presents in much of the world. Although some ice (such as that in remote inland polar regions) contains very low solute concentrations, snow in most of the world contains high concentrations of solutes such as halide salts and organic matter (OM). Solute concentrations in veins and pockets within ice and at ice surfaces can be significantly higher than in the prefrozen solution due to exclusion from the ice matrix during freezing.8 Aromatic pollutants such as pesticides and polycyclic aromatic hydrocarbons (PAHs) are found in snow both in urban centers and remote regions (e.g., ref 14). Many aromatic pollutants have carcinogenic and mutagenic properties; their toxicity often increases after photolysis (e.g., ref 15). Some recent studies have measured photolysis kinetics of aromatic pollutants in ice. Studies that probed bulk ice (or liquid regions therein) generally reported photolysis kinetics that were similar to those measured in liquid water.13,16 However, studies that probed the ice surface reported much faster photolysis © 2014 American Chemical Society

Received: January 9, 2014 Revised: February 14, 2014 Published: February 16, 2014 1638

dx.doi.org/10.1021/jp500263h | J. Phys. Chem. A 2014, 118, 1638−1643

The Journal of Physical Chemistry A

Article

hydrophobic pollutants in these organic environments may be substantially different from that in aqueous solution (e.g., ref 27). PAH photolysis is significantly slower in the waterimmiscible organic solvents octanol and decanol than in aqueous solution.28,29 However, we have recently shown that photolysis in aqueous solutions containing octanol or decanol at concentrations of several millimolar (corresponding to one to several monolayers at the water surface) proceeds at similar rates as in pure deionized water.28 This suggests that in aqueous solution PAH photolysis kinetics are regulated by total OM concentration rather than by surface excess. Organic pollutants such as PAHs are thought to be strongly associated with OM in snow and ice.21 However, the effects of OM on environmental reactions in ice have not been investigated. In this work, we examine the effects of immiscible nonchromophoric OM on the photolysis kinetics of PAHs in ice and at ice surfaces.

the best-fit line to either ln(I/I0) vs time (first-order kinetics) or I−1 vs time (second-order kinetics), where I is fluorescence intensity of the PAH after an irradiation time t and I0 is fluorescence intensity at t = 0. Fluorescence intensity was monitored at 401 nm (anthracene), 364 nm (phenanthrene), or 372 nm (pyrene). Each measurement was repeated at least three times. Fluorescence spectra. Naphthalene fluorescence spectra in ice granules were acquired at −15 °C by connecting a recirculating chiller to the sample holder of a commercial fluorimeter. Ice granules containing naphthalene were placed in a 1 cm quartz cuvette. The cuvette was placed in the fluorimeter, and emission spectra were acquired. Samples were excited at 266 nm, and fluorescence was acquired between 300 and 500 nm with 1 nm steps. Samples were allowed to sit for several minutes before spectra acquisition to achieve thermal equilibrium.

EXPERIMENTAL SECTION Sample Preparation. Samples of phenanthrene (Aldrich, ≥99.5%), pyrene (Alfa Aesar, 98%), anthracene (Acros organics, 98%), and naphthalene (Fluka, ≥99%) were prepared by stirring a few mg of solid PAH in 100 mL of water overnight and then diluting the solution to 1.2 × 10−6 M (phenanthrene), 1.0 × 10−7 M (pyrene), 6.3 × 10−8 M (anthracene), or 1.2 × 10−4 M (naphthalene). The samples were then frozen in 10 mL aliquots in ice cube trays (“ice cubes”). Some ice cubes were crushed to 2 mm diameter crystals (“ice granules”) prior to photolysis. For some experiments, aqueous solutions containing a PAH and 25 μM to 7.5 mM octanol (Acros Organics, 99%) or decanol (Alfa Aesar, ≥98%) were prepared. Samples of phenanthrene and anthracene in frozen decanol were prepared by dissolving a few mg of PAH in liquid decanol and diluting the solution to the same concentrations as described for the aqueous solutions, then freezing the solution in an ice cube tray. The resulting samples were powdery solids with diameters similar to those of the ice granules described above. Photolysis. Samples containing phenanthrene were irradiated with the output of a 450 W xenon arc lamp, and samples containing pyrene and anthracene were irradiated by a 150 W lamp. The output of the lamp passed through a 295 nm longpass cutoff filter, through a quartz flat-bottomed dish filled with deionized water acting as an IR filter, and through aluminum mesh that was used as a neutral density filter. The average lamp power reaching the sample was measured to be 26.3 mW using a power meter centered at 310 nm. The filtered output of the lamp was reflected downward onto the sample which was contained in a copper vessel. Temperatures within the vessel were varied between 23 and −25 °C (with expected variations within the sample holder of less than 1 °C) with a recirculating chiller attached to the copper vessel. Dark runs were conducted for all experiments by shielding samples from the lamp during the course of the experiment. Photolysis kinetics were determined by measuring the change in PAH fluorescence intensity over time. After a known time period of irradiation, samples were removed from the copper vessel and melted into a 1 cm quartz cuvette. This was repeated at known time intervals ranging from 1 min to 2 h. Fluorescence spectra were acquired on a commercial fluorimeter using excitation wavelengths of 252 nm for anthracene and phenanthrene and 261 nm for pyrene. Photolysis rate constants were determined from the slope of

RESULTS AND DISCUSSION Clean Ice. Spectra. Figure 1 shows naphthalene fluorescence spectra in liquid water and in ice granules with average

■

■

Figure 1. Fluorescence spectra of naphthalene in liquid water and in ice granules with diameters of 2 mm (“small granules”) and 4 mm (“large granules”). The displayed spectra are averaged from three individual samples.

diameters of 2 mm and 4 mm respectively. The surface-area-to volume (SAV) ratios of the smaller ice granules are approximately 2 times greater than the larger granules. Naphthalene emission in aqueous solution does not extend to wavelengths longer than about 390 nm, but in the ice granules significant emission is observed between 380 and 500 nm. This emission at long wavelengths is due to excimers, which form from self-associated naphthalene.30 We also acquired emission spectra of ice granules that did not contain naphthalene. The spectra did not contain features resembling monomeric or excimeric naphthalene emission. However, the sharp peaks in the ice samples in Figure 1 at approximately 340, 450, 470, and 485 nm are due to scattering from the ice rather than to naphthalene emission. Excimeric emission from naphthalene and other aromatic hydrocarbons has been measured at ice surfaces using surfacesensitive laser-induced fluorescence.17,18,31 Aromatic species are thought to self-associate at ice surfaces due to unfavorable interactions with water molecules in the disordered surface region.32 Our fluorescence measurements are not inherently selective to ice surfaces (compared to ice bulk), but we can increase our surface selectivity by increasing the SAV of our samples. Naphthalene in ice is likely distributed between the air−ice interface and liquid regions within bulk ice. As the SAV 1639

dx.doi.org/10.1021/jp500263h | J. Phys. Chem. A 2014, 118, 1638−1643

The Journal of Physical Chemistry A

Article

ratio of ice samples increases, so too does the fraction of solutes at the air−ice interface. Studies have recently shown that reaction kinetics in ice granules with high SAV ratios are similar to those measured directly at ice surfaces.12,13 The fact that we observe excimeric emission from naphthalene in ice granules and that the intensity of excimer emission relative to monomer emission intensity increases with decreasing ice granule size (i.e., with increasing SAV) indicates that we can probe naphthalene at ice surfaces using a commercial fluorimeter. Photolysis Kinetics. Table 1 shows the average photolysis rate constants of phenanthrene, pyrene, and anthracene in Figure 2. Fluorescence spectra of naphthalene in liquid water, in solid decanol, and in ice granules (2 mm diameter) prepared from deionized water and from aqueous solutions containing 2.5 mM decanol or octanol. Displayed spectra are the averaged spectra of three individual samples.

Table 1. Photolysis Rate Constants of PAHs in Water at 23 °C and in Ice Samples at −15 °C; the Stated Error Represents the Standard Deviation about the Mean for at Least Three Trials first-order rate constant (10−4 s−1) environment

phenanthrene

pyrene

anthracene

water ice cubes ice granules

0.8 ± 0.3 −a 2±1

2.3 ± 0.5 4.4 ± 0.4 3±1

1.3 ± 0.5 3±2 6±3

do not expect excimers to form at liquid or solid decanol surfaces. Figure 2 also shows the effects of incorporating 2.5 mM octanol or decanol in aqueous solutions prior to freezing on naphthalene fluorescence. In the presence of OM, excimeric naphthalene emission is observed, but to a lesser extent than in pure ice granules. This shows that OM is present at the ice surface and that it creates a physical environment that is distinct from that at pristine air−ice interfaces. In aqueous solution, an octanol monolayer is formed at the water surface at bulk concentrations of approximately 2.5 mM.33,34 We acquired naphthalene emission spectra in ice granules containing octanol concentrations ranging from 0.25 to 7.5 mM. We determined the relative degree of selfassociation at ice surfaces by taking the ratio of excimer fluorescence intensity (the total intensity from 365 to 440 nm) to monomer fluorescence intensity (310 to 335 nm). As shown in Figure 3, the degree of self-association decreases dramatically

a

Fewer than half of the experiments yielded measurable photolysis rate constants. The experiments with measurable kinetics yielded a rate constant of (5 ± 3) × 10−5 s−1. We define this rate constant as our lower limit of detection.

liquid water, ice cubes (SAV = 2.9 cm−1), and ice granules (SAV = 30 cm−1). Photolysis was better described by first-order than by second-order kinetics in all cases. Photolysis kinetics measured in ice cubes were within a factor of 2.3 of those measured in aqueous solution in all cases. This is in agreement with previous reports of similar photolysis kinetics of anthracene, phenanthrene, and pyrene in bulk ice and in aqueous solution.13,16 The photolysis rate constants we measured in ice granules were faster than those measured in aqueous solution for all three PAHs, in agreement with reports that photolysis of aromatic compounds proceeds more quickly at ice surfaces than in aqueous solution.17,19 Photolysis of anthracene and phenanthrene proceeded more quickly in ice granules than ice cubes, consistent with reactivity being different in bulk ice and at ice surfaces.12,13 Pyrene photolysis was more rapid in ice cubes than in ice granules, although photolysis in both samples was faster than in aqueous solution. We have previously observed a reduction in pyrene photolysis kinetics in aqueous solution at concentrations that exceed saturation;28 the similar kinetics in bulk ice and at ice surfaces may be due to a combination of rate-enhancing effects of the ice surface and rate-suppressing effects of pyrene selfassociation. Effects of Organics. Spectra. Figure 2 shows fluorescence spectra of naphthalene in aqueous solution, in solid decanol granules (diameter = 2 mm), and in ice granules (diameter = 2 mm). Emission from excimeric naphthalene is not observed in aqueous solution but dominates in ice granules due to selfassociation at the ice surface. No excimeric emission is observed in solid decanol. This is in agreement with an earlier study that reported only monomeric emission from naphthalene at the surface of solid decanol.17 Self-association at ice surfaces is thought to be due to unfavorable interactions between aromatic compounds and surfacial water molecules;32 since naphthalene interacts much more favorably with decanol than with water, we

Figure 3. Effects of octanol on the average excimer:monomer ratio of naphthalene in ice granules at −15 °C. The error represents the standard deviation about the mean for three samples.

in the presence of 0.25 mM octanol compared to that in pure water ice. Increasing the octanol concentration further causes only minor decreases in the ratio. The lowest excimer:monomer intensity ratio observed (at an octanol concentration of 7.5 mM) is 1.3 ± 0.5, which is approximately 6.5 times greater than the ratio measured in solid decanol (0.197 ± 0.009) and approximately 5.6 times greater than that measured in aqueous solution (0.228 ± 0.002). This suggests that in the presence of 1640

dx.doi.org/10.1021/jp500263h | J. Phys. Chem. A 2014, 118, 1638−1643

The Journal of Physical Chemistry A

Article

frozen decanol was reported to be 2.7 times faster than at the surface of liquid decanol.17 The rate constant for anthracene photolysis in liquid decanol was well below 5 × 10−5 s−1,28 so we do not expect to detect photolysis at solid decanol surfaces even with the reported rate enhancement. In bulk ice, PAH photolysis was significantly suppressed by OM, suggesting that PAHs largely resided within liquid or solid pockets of OM and were not in contact with liquid water or ice. The smaller effect of OM at ice surfaces suggests that PAHs there are still in contact with ice and do not exist completely in an organic phase. This is in agreement with the fluorescence spectra we acquired that show excimeric naphthalene emission even in ice granules containing OM concentrations corresponding to multilayer coatings in liquid solution. At the lamp powers used in our experiments, PAH photolysis kinetics depend on photon flux.13 If the presence of OM decreases the photon flux reaching the sample, this could explain the suppressed photolysis. We investigated this possibility by placing 12 mL each of octanol and water in the quartz dish used as an IR filter, forming aqueous and organic layers of approximately 3 mm in depth. The total volume of liquid in the quartz bowl was the same as in the previously described experiments. The power of the lamp passing through this dish was not significantly different from that measured when only water was in the dish, and photolysis kinetics of anthracene in aqueous solution at room temperature were similar to those measured with only water in the quartz dish. If OM suppresses PAH photolysis kinetics in ice cubes and ice granules by reducing the photon flux, we would expect the photolysis rate constant to decrease when the light passed through a layer of octanol before reaching the sample. On the basis of these results, we do not believe that nonchromophoric OM reduces PAH photolysis kinetics in ice and at ice surfaces by reducing the photon flux. The suppression of photolysis at ice surfaces in the presence of NaCl and NaBr has been ascribed to the formation of a liquid brine at the ice surface due to freezing point suppression caused by the salts.19 In that study, photolysis at the surface of frozen 100 mM NaCl solutions was half as fast as at frozen freshwater surfaces. In the current study, anthracene and phenanthrene photolysis rates were suppressed to a similar extent in the presence of less than 7.5 mM decanol or octanol; pyrene photolysis rates were suppressed even more significantly by OM. It is unlikely that OM is more than an order of magnitude more efficient at depressing water’s freezing point than NaCl. Therefore, we suggest that our results are not due primarily to surface melting, but rather are due to the formation of a distinct phase at the ice surface. This is in agreement with MD simulations which suggest that the thickness of the surfacial disordered layer is in fact reduced by organic surfactants, rather than increased as would be expected if the surface was melting.35 We investigated the effects of temperature on anthracene photolysis kinetics. Table 3 lists anthracene photolysis kinetics in ice granules at −15 and −25 °C. Reducing the temperature of pure ice samples does not affect the measured kinetics, in agreement with previous work.17 Likewise, in the presence of 7.5 mM decanol, no change in reaction rate is observed at the two temperatures. However, in the presence of 7.5 mM octanol, reducing the temperature from −15 to −25 °C decreases the photolysis rate to a value that is below our detection limit. Our estimated maximum rate constant of 5 × 10−5 s−1 indicates that the reaction is at least eight times slower at −25 °C than at −15

OM, the environment that PAHs encounter at ice surfaces is between that of the pristine ice surface and the surface of solid OM and that OM does not completely shield naphthalene from the ice surface even at multilayer coverage. This is in agreement with recent molecular dynamics (MD) simulations that predicted that octanol and other aliphatic hydrocarbons will form an organic layer above the disordered surface region of ice and that naphthalene will reside deep within the organic layer, in occasional contact with the ice surface.35 That study predicted little effect of OM films on the degree of naphthalene self-association; our results show that the effect is, in fact, significant. Photolysis Kinetics in Bulk Ice (ice cubes). We measured anthracene and pyrene photolysis kinetics in ice cubes (SAV = 2.9 cm−1) in the presence of 7.5 mM octanol or decanol. In the presence of OM, photolysis was too slow to measure. We also varied the octanol concentration in the prefrozen solution between 0.025 and 7.5 mM. No anthracene photolysis was observed in the presence of octanol at concentrations equal to or greater than 0.25 mM. In ice cubes prepared from solutions containing 0.025 mM octanol, no photolysis was observed in three of the six experiments, while the other three experiments yielded a rate constant of (3 ± 1) × 10−4 s−1, which is similar to that measured in ice cubes in the absence of OM. These results suggest that OM and PAHs are coexcluded during freezing to liquid regions within the ice, and that photolysis occurs in a primarily organic phase. The rate constants of anthracene and pyrene measured in liquid octanol and decanol are below 5 × 10−5 s−1;28,29 if photolysis kinetics are similar in ice cubes containing octanol and decanol, they will be below our detection limit. It is possible that at the lowest OM concentration (0.025 mM), PAHs in some samples are excluded to different regions than the octanol during freezing. This would explain the fact that 50% of experiments showed photolysis kinetics similar to those measured in pure ice samples, while the remaining experiments did not show any photolysis. Photolysis Kinetics at Ice Surfaces (ice granules). Table 2 summarizes the effects of octanol and decanol on the photolysis Table 2. Effects of 7.5 mM Octanol and Decanol on Photolysis Rate Constants of PAHs in Ice Granules at −15 °C; the Stated Error Represents the Standard Deviation about the Mean of at Least Three Trials measured first-order rate constants (10−4 s−1) environment

phenanthrene

pyrene

anthracene

ice ice and octanol ice and decanol solid decanol

2±1 2.0 ± 0.9 0.9 ± 0.8 −a

3±1 3±1 −a N/Ab

6±3 4±1 3±1 −a

a

Photolysis was not observed. We assign an upper limit to the rate constant of 5 × 10−5 s−1. bExperiment was not performed.

rate constants of anthracene, pyrene, and phenanthrene in ice granules (SAV = 30 cm−1). Octanol had little effect on PAH photolysis rates. The presence of 7.5 mM decanol reduced phenanthrene and anthracene photolysis rate constants by a factor of 2, and reduced pyrene photolysis rate constants to below our detection limit (so by at least a factor of 6). Phenanthrene and anthracene photolysis kinetics were also measured in frozen decanol; no photolysis was observed in these experiments. Anthracene photolysis at the surface of 1641

dx.doi.org/10.1021/jp500263h | J. Phys. Chem. A 2014, 118, 1638−1643

The Journal of Physical Chemistry A

Article

Atmospheric lifetimes of PAHs in snow at Summit, Greenland, have been reported to be much longer than laboratory-measured photolysis kinetics predict.16 It has been suggested that this could be due to PAHs being associated with soot and organic aerosols, rather than with snow and ice.16,21 Our results demonstrate that PAHs associated with an organic phase will photolyze less rapidly than those associated with a pure ice phase. These findings may help to reconcile predictions and measurements of PAH concentrations in snow and ice. Our observations that OM suppresses PAH photolysis kinetics less efficiently at ice surfaces than in liquid regions within bulk ice supports the idea that different reaction environments exist in liquid regions within bulk ice and at ice surfaces (e.g., refs 12, 13). Our results suggest that in order to accurately predict the chemical fate of organic pollutants such as PAHs in winter environments, the composition of snow and ice must be taken into account. Further, the distribution of solutes within the snow and ice must be considered, since different reaction rates (both in the presence and absence of OM) will be observed within bulk ice and at ice surfaces. Finally, we suggest that the effects of other solutes on photochemical kinetics in and on ice should be investigated to improve our understanding of environmentally relevant chemistry in solute-containing snow and ice.

Table 3. Anthracene Photolysis Kinetics in Small Ice Granules at Varying Temperatures; the Stated Error Represents the Standard Deviation about the Mean of at Least Three Trials measured first-order rate constants (10‑4 s‑1) temperature (°C)

0 mM OM

7.5 mM octanol

7.5 mM decanol

−15 −25

6±3 6±3

4±1 −a

3±1 3±1

a

Photolysis was not observed. We assign an upper limit to the rate constant of 5 × 10−5 s−1.

°C. Similarly, we were unable to measure pyrene photolysis in the presence of 7.5 mM octanol at −25 °C. This difference in octanol’s effects at the two temperatures is likely due to a change in octanol’s phase: with a melting point of −16 °C, octanol is a liquid at −15 °C and a solid at −25 °C. This suggests that the more significant suppression of PAH photolysis by decanol than octanol at −15 °C (as shown in Table 2) may be due to the fact that decanol is a solid at that temperature (mp = 6.4 °C). This would also explain the fact that octanol’s effect is greater at the lower temperature, while decanol’s effect remains unchanged. We therefore suggest that solid OM may reduce photolysis kinetics more significantly than liquid OM. The reason for this behavior is not clear. It is possible that solid OM reduces photolysis kinetics by sequestering the PAHs from the underlying ice surface more effectively than liquid OM. However, naphthalene excimer:monomer ratios in ice granules containing octanol were lower than those containing the same concentration of decanol at −15 °C, indicating that the liquid OM (octanol) sequestered the PAH more effectively than the solid OM (decanol). Further, excimer:monomer ratios in ice granules containing 7.5 mM octanol were larger at −25 °C than at −15 °C (1.9 ± 0.7 and 1.3 ± 0.5, respectively), which again suggests that naphthalene has more contact with the ice surface when octanol is in the solid rather than in the liquid phase. The enhanced suppression of photolysis by solid OM may have implications for the fate of PAHs in snow associated with particulate organic matter versus dissolved organic matter, and warrants further study.

■

AUTHOR INFORMATION

Corresponding Author

*Telephone: (315) 443-3285. Fax: (315) 443-4070. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The authors thank Drs. M. S. Braiman, B. S. Hudson, I. V. Korendovych, M. M. Maye, and K. Ruhlandt for the use of scientific equipment.

■

■

REFERENCES

(1) Abbatt, J. P. D.; Thomas, J. L.; Abrahamsson, K.; Boxe, C.; Granfors, A.; Jones, A. E.; King, M. D.; Saiz-Lopez, A.; Shepson, P. B.; Sodeau, J.; et al. Halogen Activation Via Interactions with Environmental Ice and Snow in the Polar Lower Troposphere and Other Regions. Atmos. Chem. Phys. 2012, 12, 6237−6271. (2) Bartels-Rausch, T. Ten Things We Need to Know About Ice and Snow. Nature 2013, 494, 27−29. (3) Domine, F.; Albert, M.; Huthwelker, T.; Jacobi, H. W.; Kokhanovsky, A. A.; Lehning, M.; Picard, G.; Simpson, W. R. Snow Physics as Relevant to Snow Photochemistry. Atmos. Chem. Phys. 2008, 8, 171−208. (4) Grannas, A. M.; Jones, A. E.; Dibb, J.; Ammann, M.; Anastasio, C.; Beine, H. J.; Bergin, M.; Bottenheim, J.; Boxe, C. S.; Carver, G.; et al. An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts. Atmos. Chem. Phys. 2007, 7, 4329−4373. (5) McNeill, V. F.; Grannas, A. M.; Abbatt, J. P. D.; Ammann, M.; Ariya, P.; Bartels-Rausch, T.; Domine, F.; Donaldson, D. J.; Guzman, M. I.; Heger, D.; et al. Organics in Environmental Ices: Sources, Chemistry, and Impacts. Atmos. Chem. Phys. 2012, 12, 9653−9678. (6) Simpson, W. R.; von Glasow, R.; Riedel, K.; Anderson, P.; Ariya, P.; Bottenheim, J.; Burrows, J.; Carpenter, L.; Friess, U.; Goodsite, M. E.; et al. Halogens and Their Role in Polar Boundary-Layer Ozone Depletion. Atmos. Chem. Phys. Discuss. 2007, 7, 4285−4403. (7) Dash, J. G.; Rempel, A. W.; Wettlaufer, J. S. The Physics of Premelted Ice and Its Geophysical Consequences. Rev. Mod. Phys. 2006, 78, 695−741.

CONCLUSIONS AND ATMOSPHERIC IMPLICATIONS We have investigated the effects of nonchromophoric OM on the physical environment encountered by PAHs associated with ice, and to its effects on PAH photolysis kinetics in bulk ice and at ice surfaces. Our results suggest that OM can create unique reaction environments within bulk ice and at ice surfaces and can alter PAH reactivity. Nonchromophoric OM reduces PAH photolysis kinetics significantly in bulk ice, and to varying degrees at ice surfaces. Solid OM appears to suppress photolysis more effectively than liquid OM. This could result in an apparent temperature dependence to PAH photolysis in the environment, since photolysis will become slower as the temperature decreases and OM in contact with the PAHs changes phase from liquid to solid. These results show that photolysis in “dirty” ice, such as is present in most cities, may occur quite differently than in pristine ice, which has been primarily used in laboratory experiments. The results also show that OM does not need to absorb sunlight in order to affect pollutant photolysis kinetics. To our knowledge this possibility has not previously been considered. 1642

dx.doi.org/10.1021/jp500263h | J. Phys. Chem. A 2014, 118, 1638−1643

The Journal of Physical Chemistry A

Article

(8) Bartels-Rausch, T.; Jacobi, H. W.; Kahan, T. F.; Thomas, J. L.; Thomson, E. S.; Abbatt, J. P. D.; Ammann, M.; Blackford, R. R.; Bluhm, H.; Boxe, C.; et al. A Review of Air−Ice Chemical and Physical Interactions (AICI): Liquid, Quasi-Liquid, and Solid Ice in Snow. Atmos. Chem. Phys. 2014, 14, 1587−1633. (9) Dash, J. G.; Fu, H. Y.; Wettlaufer, J. S. The Premelting of Ice and Its Environmental Consequences. Rep. Prog. Phys. 1995, 58, 115−167. (10) Wettlaufer, J. S.; Worster, M. G. Premelting Dynamics. Annu. Rev. Fluid Mech. 2006, 38, 427−452. (11) Rosenberg, R. Why Is Ice Slippery? Phys. Today 2005, 58, 50− 55. (12) Kahan, T. F.; Zhao, R.; Donaldson, D. J. Hydroxyl Radical Reactivity at the Air−Ice Interface. Atmos. Chem. Phys. 2010, 10, 843− 854. (13) Kahan, T. F.; Zhao, R.; Jumaa, K. B.; Donaldson, D. J. Anthracene Photolysis in Aqueous Solution and Ice: Photon Flux Dependence and Comparison of Kinetics in Bulk Ice and at the Air-Ice Interface. Environ. Sci. Technol. 2010, 44, 1302−1306. (14) Grannas, A. M.; Bogdal, C.; Hageman, K. J.; Halsall, C.; Harner, T.; Hung, H.; Kallenborn, R.; Klan, P.; Klanova, J.; Macdonald, R. W.; et al. The Role of the Global Cryosphere in the Fate of Organic Contaminants. Atmos. Chem. Phys. 2013, 13, 3271−3305. (15) Finlayson-Pitts, B. J.; Pitts, J. N., Chemistry of the Upper and Lower Atmosphere; Academic Press: San Diego, 2000; p 969. (16) Ram, K.; Anastasio, C. Photochemistry of Phenanthrene, Pyrene, and Fluoranthene in Ice and Snow. Atmos. Environ. 2009, 43, 2252−2259. (17) Kahan, T. F.; Donaldson, D. J. Photolysis of Polycyclic Aromatic Hydrocarbons on Water and Ice Surfaces. J. Phys. Chem. A 2007, 111, 1277−1285. (18) Kahan, T. F.; Donaldson, D. J. Benzene Photolysis on Ice: Implications for the Fate of Organic Contaminants in the Winter. Environ. Sci. Technol. 2010, 44, 3819−3824. (19) Kahan, T. F.; Kwamena, N. O. A.; Donaldson, D. J. Different Photolysis Kinetics at the Surface of Frozen Freshwater Vs. Frozen Salt Solutions. Atmos. Chem. Phys. 2010, 10, 10917−10922. (20) Klanova, J.; Klan, P.; Heger, D.; Holoubek, I. Comparison of the Effects of UV, H2O2/UV and γ-Irradiation Processes on Frozen and Liquid Water Solutions of Monochlorophenols. Photochem. Photobiol. Sci. 2003, 2, 1023−1031. (21) Domine, F.; Bock, J.; Voisin, D.; Donaldson, D. J. Can We Model Snow Photochemistry? Problems with the Current Approaches. J. Phys. Chem. A 2013, 117, 4733−4749. (22) Mmereki, B. T.; Chaudhuri, S. R.; Donaldson, D. J. Enhanced Uptake of PAHs by Organic-Coated Aqueous Surfaces. J. Phys. Chem. A 2003, 107, 2264−2269. (23) Donaldson, D. J.; Vaida, V. The Influence of Organic Films at the Air-Aqueous Boundary on Atmospheric Processes. Chem. Rev. 2006, 106, 1445−1461. (24) Donaldson, D. J.; Valsaraj, K. T. Adsorption and Reaction of Trace Gas-Phase Organic Compounds on Atmospheric Water Film Surfaces: A Critical Review. Environ. Sci. Technol. 2010, 44, 865−873. (25) Schwier, A.; Mitroo, D.; McNeill, V. F. Surface Tension Depression by Low-Solubility Organic Material in Aqueous Aerosol Mimics. Atmos. Environ. 2012, 54, 490−495. (26) Park, S.-C.; Burden, D. K.; Nathanson, G. M. Surfactant Control of Gas Transport and Reactions at the Surface of Sulfuric Acid. Acc. Chem. Res. 2009, 42, 379−387. (27) Hassett, J. P. Chemistry: Dissolved Natural Organic Matter as a Microreactor. Science 2006, 311, 1723−1724. (28) Grossman, J.; Kirrich, M.; Stern, A.; Kahan, T. F., Photolysis Kinetics of Aqueus-Phase Polycyclic Aromatic Hydrocarbons in the Presence of Organic Matter and Halide Salts In preparation. (29) Donaldson, D. J.; Kahan, T. F.; Kwamena, N.-O. A.; Handley, S. R.; Barbier, C. Atmospheric Chemistry of Urban Surface Films. ACS Symp. Ser. 2009, 1005, 79−90. (30) Kawakubo, T.; Okada, M.; Shibata, T. Excimer (Excited Dimer) Fluorescence of Naphthalene at 77 K in Rigid Media. J. Phys. Soc. Jpn. 1966, 21, 1469−1470.

(31) Kahan, T. F.; Donaldson, D. J. Heterogeneous Ozonation Kinetics of Phenanthrene at the Air-Ice Interface. Environ. Res. Lett. 2008, 3, 045006. (32) Ardura, D.; Kahan, T. F.; Donaldson, D. J. Self-Association of Naphthalene at the Air-Ice Interface. J. Phys. Chem. A 2009, 113, 7353−7359. (33) Mmereki, B. T.; Donaldson, D. J. Direct Observation of the Kinetics of an Atmospherically Important Reaction at the Air− Aqueous Interface. J. Phys. Chem. A 2003, 107, 11038−11042. (34) Lin, S. Y.; Wang, W. J.; Hsu, C. T. Adsorption Kinetics of 1Octanol at the Air-Water Interface. Langmuir 1997, 13, 6211−6218. (35) Liyana-Arachchi, T. P.; Valsaraj, K. T.; Hung, F. R. Adsorption of Naphthalene and Ozone on Atmospheric Air/Ice Interfaces Coated with Surfactants: A Molecular Simulation Study. J. Phys. Chem. A 2012, 116, 2519−2528.

1643

dx.doi.org/10.1021/jp500263h | J. Phys. Chem. A 2014, 118, 1638−1643